Biphenyl-substituted triazines

ABSTRACT

Biphenyl-substituted triazines of the formulaewhich are notable for high thermal stability, are used as stabilizers for organic polymers to counter damage thereto caused by light, oxygen and heat, as light stabilizers for textile fiber materials and as sunscreens for the human skin.

This is a divisional of application Ser. No. 09/383,163, filed Aug. 25,1999, now U.S. Pat. No. 6,255,483, which is a continuation-in-part ofapplication Ser. No. 08/913,214, filed Sep. 10, 1997, abandoned.

The present invention relates to biphenyl-substituted triazinecompounds, to processes for the preparation of these compounds, toorganic material stabilized with the aid of these compounds againstdamage by sunlight, heat and oxygen, to the corresponding use of thesecompounds as stabilizers for organic material, and to their use as lightstabilizers for textile fiber materials and as sunscreens for the humanskin.

If it is desired to increase the light stability of an organic material,especially a coating, a light stabilizer is usually added. A class oflight stabilizers which is very frequently employed comprises the UVabsorbers, which protect the material by absorbing the harmful radiationvia chromophores. An important group of UV absorbers is thetriphenyltriazines, as are described inter alia in EP-A-434 608,EP-A-520 938, U.S. Pat. No. 4,619,956, EP-A-483 488, EP-A-500 496,EP-A-502 816 and EP-A-506 615. Some bis-resorcinyl derivatives from thisgroup are mentioned, for example, in CH-A-480 090, CH-A-484 695, U.S.Pat. No. 3,249,608, U.S. Pat. No. 3,244,708, U.S. Pat. No. 3,843,371,U.S. Pat. No. 4,826,978, EP-A-434 608, EP-A-520 938, GB-A-2 273 498 andWO-A-94/18 278.

It has now been found that certain biphenyl-substituted triazinecompounds have surprisingly high absorption in the range from 300 to 400nm which is important for organic polymers.

The novel biphenyl-substituted triazine compounds are of the formula

in which

R₁ is hydrogen; C₁-C₂₄alkyl or C₅-C₁₂cycloalkyl; or C₁-C₂₄alkyl orC₅-C₁₂cycloalkyl, which are substituted by 1 to 9 halogen atoms, —R₄,—OR₅, —N((R₅)₂, ═NR₅, ═O, —CON(R₅)₂, —COR₅, —COOR₅, —OCOR₅, —OCON(R₅)₂;—CN, —NO₂, —SR₅, —SOR₅, —SO₂R₅, —P(O)(OR₅)₂, a morpholinyl, piperidyl,2,2,6,6-tetramethylpiperidyl, piperazinyl or N-methylpiperazinyl group,or combinations thereof; and/or C₁-C₂₄alkyl or C₅-C₁₂cycloalkyl which isinterrupted by 1 to 6 phenylene, —O—, —NR₅—, —CONR₅—, —COO—, —OCO—,—CH(R₅)—, —C(R₅)₂— or —CO— groups or combinations thereof; and R₁ isfurthermore C₂-C₂₄alkenyl; halogen; —SR₃, SOR₃; SO₂R₃; —SO₃H; —SO₃M; ora radical of the formula

R₃ is C₁-C₂₀alkyl; C₃-C₁₈alkenyl; C₅-C₁₂cycloalkyl; C₇-C₁₅phenylalkyl,or C₆-C₁₂aryl which is unsubstituted or substituted by 1 to 3 C₁-C₄alkylgroups;

R₄ is unsubstituted C₆-C₁₂aryl; or C₆-C₁₂aryl which is substituted by 1bis 3 halogen atoms, C₁-C₈alkyl or C₁-C₈alkoxy or combinations thereof;C₅-C₁₂cycloalkyl; unsubstituted C₇-C₇-C₁₅-phenylalkyl; orC₇-C₁₅phenylalkyl which is substituted in the phenyl ring by 1 to 3halogen atoms, C₁-C₈alkyl, C₁-C₈alkoxy or combinations thereof orC₂-C₈alkenyl;

R₅ is R₄; hydrogen; C₁-C₂₄alkyl; or a radical of the formula

 in which

T is hydrogen; C₁-C₈alkyl; C₂-C₈alkyl which is substituted by one ormore hydroxyl groups or by one or more acyloxy groups; oxyl; hydroxyl;—CH₂CN;, C₁C₁₈alkoxy; C₅-C₁₂cycloalkoxy; C₃-C₆alkenyl; C₇-C₉phenylalkyl;C₇-C₉phenylalkyl which is substituted one, two or three times in thephenyl ring by C₁-C₄alkyl; or aliphatic C₁-C₈alkanoyl;

R₆ to R₁₅ independently of one another are hydrogen; hydroxyl; —C≡N;C₁-C₂₀alkyl; C₁-C₂₀-alkoxy; C₇-C₂₀phenylalkyl; C₄-C₁₂cycloalkyl;C₄-C₁₂cycloalkoxy; halogen; halo-C₁-C₅-alkyl; sulfonyl; carboxyl;acylamino; acyloxy; C₁-C₁₂alkoxycarbonyl; aminocarbonyl; —O—Y; or O—Z;or R₈ and R₉, together with the phenyl radical, are a cyclic radicalwhich is interrupted by one or more oxygen or nitrogen atoms;

M is alkali metal;

p 1 or 2;

q 0 or 1;

and, if q is 0, R₁₂ and R₁₃ are not hydroxyl;

if p is 1,

X, Y and Z independently of one another are hydrogen; C₄-C₅₀alkyl whichis interrupted by one or more oxygen atoms and/or substituted by one ormore hydroxyl groups;

 C₄-C₁₂cycloalkyl which is substituted by R₂; —OR₂-substitutedC₄-C₁₂cycloalkyl; —CH((CH₂)_(n)—R₂)—CO—O—(CH₂)_(m)—R′₂;—CH((CH₂)_(n)—R₂)—CO—(NR′)—(CH₂)_(m)—R′₂;

 —CO—(CH₂)_(n)—R₂; —CO—O—(CH₂)_(n)—R₂, —CH₂—CH(—O(CO)—R₂)—R′₂,—CO—NR′—(CH₂)_(n)—R₂; C₆-C₁₂aryl; allyl; C₄-C₂₀alkenyl which isunsubstituted or is interrupted by one or more oxygen atoms;C₄-C₁₂cycloalkenyl which is unsubstituted or is substituted by one ormore oxygen atoms; C₃-C₂₀alkynyl; or C₆-C₁₂cycloalkynyl;

R₂ and R′₂ independently of one another are R_(x) if attached to acarbon atom and are R_(y) if attached to an atom other than carbon;

n 0 to 20;

m 0 to 20;

and, if p is 2,

Y and Z independently of one another are as defined for when p is 1; and

X is C₂-C₁₂alkylene; —CO—(C₂-C₁₂alkylene)—CO—; —CO-phenylene-CO—;CO-biphenylene-CO—; CO—O—(C₂-C₁₂alkylene)—O—CO—; —CO—O-phenylene-O—CO—;—CO—O-biphenylene-O—CO—; —CO—NR′—(C₂-C₁₂alkylene)—NR′—CO—;—CO—NR′-phenylene-NR′—CO—; —CO—NR′-biphenylene-NR′—CO—; —CH₂—CH(OH)—CH₂—; —CH₂—CH(OR₂) —CH₂—; —CH₂—CH(OH)—CH₂—O—D—O—CH₂—CH(OH)—CH₂;—CH₂—CH(OR₂)—CH₂—O—D—O—CH₂—CH(OR₂)—CH₂—;

D is C₂-C₁₂alkylene; C₄-C₅₀alkylene which is interrupted by one or moreoxygen atoms; phenylene; biphenylene or phenylene-E-phenylene;

E is —O—; —S—; —SO₂—; —CH₂—; —CO—; or —C(CH₃)₂—;

R_(x) is hydrogen; hydroxyl; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl;C₁-C₂₀alkoxy; C₄-C₁₂cycloalkoxy; C₄-C₁₂cycloalkyl or C₄-C₁₂cycloalkoxywhich is interrupted by one or more oxygen atoms; C₆-C₁₂aryl;hetero-C₃-C₁₂aryl; —OR_(z); NHR_(z); R_(z); CONR′R″; allyl;C₂-C₂₀alkenyl; C₄-C₁₂-cycloalkenyl which is uninterrupted or interruptedby one or more oxygen atoms; C₃-C₂₀alkynyl; or C₆-C₁₂cycloalkynyl;

R_(y) is hydrogen; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl which is uninterruptedor interrupted by one or more oxygen atoms; C₆-C₁₂aryl;hetero-C₃-C₁₂aryl; R_(z); allyl; C₂-C₂₀alkenyl; C₄-C₁₂-cycloalkenylwhich is uninterrupted or is interrupted by one or more oxygen atoms;C₃-C₂₀alkynyl; or C₆-C₁₂cycloalkynyl;

R_(z) is —COR′; —COOR′; —CONR′R″; —CO—CH═CH₂; —CO—C(CH₃)═CH₂;

R′ and R″ independently of one another are hydrogen; C₁-C₂₀alkyl;C₄-C₅₀alkyl which is interrupted by one or more oxygen atoms;C₄-C₁₂cycloalkyl which is uninterrupted or interrupted by one or moreoxygen atoms; C₂-C₂₀alkenyl which is unsubstituted or is interrupted byone or more oxygen atoms; or C₆-C₁₂aryl.

The radicals R_(x), R_(y), R′ and R″ can independently of one another besubstituted by hydroxyl, —NH₂, —NHR′, —NR′R″, halogen, C₁-C₂₀alkyl,C₁-C₂₀alkoxy, C₄-C₁₂cycloalkyl, C₄-C₁₂cycloalkoxy, C₂-C₂₀alkenyl,C₄-C₁₂cycloalkyl, C₃-C₂₀alkynyl, C₆-C₁₂cycloalkynyl, C₆-C₁₂aryl,acylamine, acyloxy, sulfonyl, carboxyl, (meth)acryloxy,(meth)acrylamino,

The above-mentioned radicals can also constitute isomer mixtures fromthe definitions given. When q is 0, compounds are preferred wherein noneof R₆ to R₁₅ is OH or allyloxy, especially wherein none is OH oralkenyloxy.

Alkyl is branched or unbranched alkyl, such as methyl, ethyl, propyl,isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl,n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

C₁-C₂₀alkoxy comprises straight-chain or branched radicals such as, forexample, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy,heptyloxy, octyloxy, isooctyloxy, nonyloxy, undecyloxy, dodecyloxy,tetradecyloxy or pentadecyloxy, hexadecyloxy, heptadecyloxy,octadecyloxy, nonadecyloxy or eicosyloxy.

Phenylalkyl is alkyl which is substituted by phenyl. C₇-C₂₀phenylalkyl,for example, comprises benzyl, α-methylbenzyl, α,α-dimethylbenzyl,phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl,phenylheptyl, phenyloctyl, phenylnonyl, phenyldecyl, phenyidodecyl orphenyltetradecyl.

Halogen is —F, —Cl, —Br or —I; preference is given to —F or —Cl,especially —Cl.

C₄-C₁₂cycloalkyl is for example cyclobutyl, cyclopentyl, cycloheptyl,cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclodocecyl and, inparticular cyclohexyl.

Examples of C₄-C₁₂cycloalkyl interrupted by one or more oxygen atoms aretetrahydrofuryl, 1-oxa-4-cyclohexyl and 1,3-dioxa-4-cyclohexyl.

Within the scope of the definitions given alkenyl includes allyl,isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl,3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl,n-dodec-2-enyl and n-octadec-4-enyl, inter alia. C₂-C₂₀alkenyl is mostpreferably allyl or vinyl when bonded to a carbon atom, and allyl whenbonded to a non-carbon atom.

Acyl is the residue of an aliphatic, cycloaliphatic or aromaticcarboxylic acid preferably of 2-20 carbon atoms. Preferred areC₂-C₁₈alkanoyl, C₃-C₈alkenoyl, or the residue of a C₇-C₁₂phenylcarboxylic acid like benzoic acid, methylbenzoic acid, phenylacetic acidor cinnamic acid.

C₂-C₁₈alkanoyl is for example acetyl, propionyl, acryloyl, methacryloylor benzoyl.

C₃-C₈alkenoyl is for example acryloyl or methacryloyl.

C₅-C₁₂cycloalkenyl is for example 2-cyclopenten-1-yl,2,4-cyclopentadien-1-yl-, 2-cyclohexen-1-yl, 2-cyclohepten-1-yl or2-cycloocten-1-yl.

C₄-C₁₂cycloalkoxy is for example cyclobutyloxy, cyclopentyloxy,cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy,cyclodecyloxy, cycloundecyloxy, cyclododecyloxy, especiallycyclohexyloxy.

Particular examples of C₆-C₁₂aryl are phenyl, naphthyl and biphenyl.

Hetero-C₃-C₁₂aryl is preferably pyridyl, pyrimidinyl, triazinyl,pyrrolyl, furyl, thiophenyl or quinolyl.

A cyclic radical formed by R₁₁ and R₁₂ together with the phenyl radicalis mainly one containing 2-4 carbon atoms; an example is3,4-dimethylenedioxyphenyl.

Preferred compounds according to the invention are of the formula

and in particular of the formula

in which

R₁, X, Y, Z and p are as defined for formula (1).

Among the compounds of the formula (3) or (3a), preference is given tothose in which

X is ((CH₂)_(m)—CH₂—O—)_(n)—R_(y); —(CH₂)_(n)—R_(x);—CH₂—CH(OH)—CH₂—O—(CH₂)_(n)—R_(x);

R_(x) is hydrogen; hydroxyl; C₁-C₂₀alkyl; or C₄-C₁₂cycloalkyl;

R_(y) is hydrogen; or C₁-C₂₀alkyl; or C₄-C₁₂cycloalkyl;

m is 0 to 20;

n is 0 to 20;

p is 1; and

R₁ is as defined in formula 1.

Very particular preference attaches to triazine compounds of theformulae (1) to (3) and (1a) to (3a) in which

X, Y and Z independently of one another are hydrogen,—((CH₂)_(m)—CH₂—O—)_(n)—R₂; —(CH₂—CH((CH₂)_(m)—R₂)—O—)_(n)—R′₂;—(CH((CH₂)_(m)—R₂)—CH₂—O—)_(n)—R′₂; —(CH₂)_(n)—R₂;—CH₂—CH(OH)—CH₂—O—(CH₂)_(n)—R₂; —CH₂—CH(OR₂)—CH₂—O—(CH₂)_(n)—R′₂;—CH₂—CH(OH)—CH₂—O—(CH₂)_(n)—OR₂; or —CH₂—CH(OR₂)—CH₂—O—(CH₂)_(n)—OR′₂;

Further preferred compounds are those of the formula

in which

R₁ is hydrogen; C₁-C₂₀alkyl; C₁-C₂₀alkoxy; or halogen;

R₁₄ is hydrogen; C₁-C₂₀alkyl; C₁-C₂₀alkoxy; phenyl-C₁-C₂₀alkoxy; orhalogen;

R₁₂ is hydrogen; C₁-C₂₀alkyl; C₁-C₂₀alkoxy; or halogen;

R₆ and R₈, independently of one another are hydrogen; C₁-C₂₀alkyl;C₁-C₂₀alkoxy, or halogen; and

q is 0 or 1.

Particularly preferred are those compounds of the formula (4a) in which

R₁ is hydrogen; C₁-C₂₀alkyl; or C₁-C₂₀alkoxy;

R₁₃, R₁₄, R₁₅ and R₁₆ are hydrogen; and

q is 0 or 1.

The compounds of the formulae (1) to (4) and (1a) to (4a) are novelcompounds; examples of the novel compounds include2-(2-hydroxyphenyl)-4-phenyl-6-(4-biphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(4-biphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-biphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropyloxy)phenyl]-4,6-bis(4-biphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-tridecyloxypropyloxy)phenyl]-4,6-bis(4-biphenyl)-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4-(2,4-dimethoxyphenyl)-phenyl-6-(4-biphenyl)-1,3,5-triazine,2,4-bis(2-hydroxyphenyl)-6-(4-biphenyl)-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(2-methoxyphenyl)-6-(4-biphenyl)-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-(4-biphenyl)-1,3,5-triazine;or 2-(2-hydroxy-4-methoxyphenyl)-4-6-bis(4-biphenyl)-1,3,5-triazine.

The novel compounds of the formulae (1) to (4) and (1a) to (4a) can beprepared in various ways.

For example, these compounds can be prepared in accordance with or inanalogy to one of the methods indicated in EP-A-434 608 or in thepublication by H. Brunetti and C. E. Lüthi, Helv. Chim. Acta 55, 1566(1972), by Friedel-Crafts Addition of Halotriazines onto appropriatephenols. This may be followed by further reaction in accordance withknown methods to give compounds of the formulae (1) to (4) and (1a) to(4a). Such reactions and methods are described, for example, in EP-A-434608, page 15, line 11 to page 17, line 1.

The novel compounds can also be prepared from the correspondingbenzamidine compounds of the formula

with a salicylic compound of the formula

to give the triazine compound of the formula (1), where

Hal₁ is halogen;

r is 0 or 1;

X₁ is halogen or —OR₅;

R₅ is C₁-C₃alkyl; and

R₁, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, q and X are as definefor formula (1).

Analogous reactions are described, for example, in EP-A-0 649 841.

The novel compounds of the formula (1) or (1a) can also be prepared bydehydrogenating the corresponding dihydrotriazine compound of theformula

in which R₁, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, X, p and qare as defined for formula (1).

An example of the dehydrogenating agents which can be employed ischloranil. The dehydrogenation of dihydrotriazine compounds to give1,3,5-triazines using chloranil is known, for example, from Khim.Geteritsikl. Soedin. (2), pp.350-353 (1969).

Other dehydrogenating agents which can be used for the present processare reducing agents which are known per se, for example dithionites,pyrosulfates, sulfites and thiosulfites, but which in this case act asoxidizing agents. This preparation variant is preferably carried outusing sodium bisulfite or sodium dithionite. This process is described,for example, in EP-A-0 648 754.

The dihydrotriazines of the formulae (8) and (8a) are novel compounds.The invention additionally relates to these novel compounds.

The novel dihydrotriazine compounds, disubstituted by biphenyl, of theformula (8) or (8a), i.e. those for which q is 1 and p is 1 in formula(8) or (8a), are prepared by, for example, reacting the benzamidinecompounds of the formula (5) and (6) with one mole of anα-hydroxybenzaldehyde of the formula

R₁ and X are as defined for formula (1); and

r is 0 or 1.

The novel biphenyl-substituted triazine compounds can also be preparedfrom the corresponding benzoxazinones of the formula

and a benzamidine compound of the formula (6).

In formula (10), R₁, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, q and X are as defined forformula (1); and r is 0 or 1.

The reaction is generally carried out in unsubstituted or substitutedC₁-C₅ alcohols, for example methylcellosolve, at a temperature from 0 to100° C., preferably from 40 to 80° C. In general, at least thecalculated quantity of a base is added in order to neutralize the acidwhich forms during the reaction. Bases which can be used include bothorganic and inorganic compounds, for example alkali metal hydroxide,especially sodium hydroxide or potassium hydroxide solution; aqueousammonia solution; ammonia gas; alkali metal carbonate, especially sodiumcarbonate or potassium carbonate; sodium acetate; tertiary amines, suchas pyridine or trialkylamines, especially triethylamine,N,N-dimethylcyclohexylamine, N,N-dimethylaniline; alkali metalalkylates, especially sodium methylate and potassium methylate orpotassium tertbutylate.

The benzoxazinone compounds of the formula (10) are novel compounds. Thepresent invention additionally relates to these compounds.

The novel benzoxazinone compounds of the formula (10) are accessible,for example, by acidcatalyzed cyclization of salicylamides of theformula

The synthesis can be carried out as a one-pot reaction by reacting thesalicylamide with the carbonyl halide of the formula

in, for example, boiling aromatic solvents, for example xylene ortoluene. The reaction time in this case is from 1 to 10 hours,preferably from: 2 to 4 hours.

In formulae (11) and (12) R₁, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, q, r, X and Halare as defined.

In analogy to the literature as represented by H. J. Kabbe, K. Eiter andF. Möller, Liebigs Ann. Chem. 704, 140-143, (1967) it is possible toprepare 2-amino-4,6-bis(4-biphenyl)-1,3,5-triazine of the formula

starting from 4-biphenylnitrile and a guanidine salt. The amino groupcan then be hydrolyzed with sodium hydroxide solution to the hydroxylgroup. Subsequent reaction of SOCl₂ gives the compound of the formula(114) (Example 14), which can then be reacted as described to give thecompound of the formula (115) (Example 15).

The novel biphenyl-substituted triazine compounds are very good UVabsorbers which are particularly notable for high thermal stability.They are therefore used as stabilizers for organic polymers, especiallycoating materials, against damage thereto by light, oxygen and heat, andas light stabilizers for textile fiber materials.

Particular advantages of the novel biphenyl-substituted compoundsinclude their surprisingly high absorption in the 300 to 400 nm regionof the electromagnetic spectrum. Another surprising finding is that thebehaviour of the solubility and melting points of the novel compoundsis, despite the large conjugated aromatic system, similar to that of thesolubility and melting points of comparable compounds from the priorart. Material stabilized with the compounds according to the inventionfeatures outstanding resistance to the effects of weathering and light,and outstanding photostability of the incorporated stabilizer.

The materials to be stabilized can for example be oils, fats, waxes,cosmetics or biocides. A particularly interesting application is inpolymeric materials as are present in plastics, rubbers, paints andother coating materials, photographic material or adhesives. Examples ofpolymers and other substrates which can be stabilized in this way arethe following:

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for example ofcyclopentene or norbornene; furthermore polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE),polyethylene of high density and high molecular mass (HDPE-HMW),polyethylene of high density and ultra-high molecular mass (HDPE-UHMW),medium density polyethylene (MDPE), low density polyethylene (LDPE),linear low density polyethylene (LLDPE), branched low densitypolyethylene (BLDPE).

Polyolefins, i.e. polymers of monoolefins exemplified in the precedingparagraph, in particular polyethylene and polypropylene, can be preparedby different, and especially by the following, methods:

a) radical polymerization (normally under high pressure and at elevatedtemperature)

b) catalytic polymerization using a catalyst that normally contains oneor more metals of group IVb, Vb, VIb or VIII of the Periodic Table.These metals usually have one or more ligands, such as oxides, halides,alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls thatmay be either π- or σ-coordinated. These metal complexes may be in thefree form or fixed on substrates, for example on activated magnesiumchloride, titanium(III) chloride, alumina or silicon oxide. Thesecatalysts may be soluble or insoluble in the polymerization medium. Thecatalysts can be activated by themselves in the polymerization orfurther activators may be used, for example metal alkyls, metalhydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes,the metals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified, for example, with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedunder 1), for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acidcopolymers, LLDPE/ethylene-vinyl acetate copolymers,LLDPE/ethylene-acrylic acid copolymers and alternating or randompolyalkylenelcarbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene poly-(p-methylstyrene), poly-(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrenelalkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/propylene/diene terpolymer, and blockcopolymers of styrene such as styrene/butadiene/styrene,styrene/isoprene/styrene, styrenelethylene/butylene/styrene orstyrenelethylene/propylene/styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene, styrene andalkyl acrylates or alkyl methacrylates on polybutadiene, styrene andacrylonitrile on ethylene/propylene/diene terpolymers, styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers mentioned under 6), for example thecopolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubber, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride; polyvinylidene fluoride; as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates, polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate copolymers, acrylonitrile/vinylhalide copolymers or acrylonitrile/alkyl methacrylate/butadieneterpolymers.

11. Polymers derived from unsaturated alcohols and amines of the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in point 1.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain comonomers, for example ethylene oxide; polyacetalsmodified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures thereof with styrenepolymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters and polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6,12/12, polyamide 11, polyamide 12, aromatic polyamides starting fromm-xylene, diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic and/or terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide. Block copolymers of the aforementioned polyamides withpolyolefins, olefin copolymers, ionomers or chemically bonded or graftedelastomers; or with polyethers, e.g. with polyethylene glycol,polypropylene glycol or polytetramethylene glycol. As well as polyamidesor copolyamides modified with EPDM or ABS; and polyamides condensedduring processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalates and polyhydroxybenzoates,as well as block polyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, urea or melamine on the other hand, such as phenol/formaldehyderesins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample from epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates,polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic or aromatic glycidyl compounds, for example products ofbisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which arecrosslinked by means of customary hardeners, for example anhydrides oramines, with or without accelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/tPP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The invention therefore also relates to a composition comprising

(A) an organic material which is sensitive to damage by light, oxygenand/or heat, and

(B) as stabilizer, a compound of the formula (1) or (1a).

The invention also relates to a process for stabilizing organic materialagainst damage by light, oxygen and/or heat, which comprises addingthereto, as stabilizer, a compound of the formula (1) or (1a), and tothe use of the compound of the formula (1) or (1a) for stabilizingorganic material.

The amount of the stabilizer to be used depends on the organic materialto be stabilized and on the intended use of the stabilized material. Ingeneral, the novel composition comprises from 0.01 to 15 parts byweight, in particular from 0.05 to 10 parts by weight, especially from0.1 to 5 parts by weight, of the stabilizer (component B) per 100 partsby weight of component (A).

The stabilizer (component (B)) can also be a mixture of two or morecompounds of the formulae (1) and (1a). In addition to the novelcompounds, the novel compositions can also comprise other stabilizers orother additives, for example antioxidants, further light stabilizers,metal deactivators, phosphites or phosphonites. Examples of thesestabilizers are the following:

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor are branched in the side chain, such as, for example,2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundec-1-yl)-phenol,2,4-dimethyl-6-(1-methylheptadec-1-yl)-phenol, 2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4-thiobis(3,6-di-sec-amylphenol),4,4-bis(2,6-dimethyl-4-hydroxyphenyl)-disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methylpheny)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,di-[4-(1,1,3,3-tetramethylbutyl)phenyl]2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurat,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for example dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt ofthe monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxalamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)-oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis-(hydroxyethyl)oxalamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

1.18. Ascorbic acid (Vitamin C).

1.19. Aminic antioxidants, for exampleN,N′-diisopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-di-(naphthyl-2)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclo-hexyl-N′-phenyl-p-phenylenediamine,4-(p-toluene-sulfonamido)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyidiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, di-(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethylphenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-di-[(2-methylphenyl)amino]ethane, 1,2-di-(phenylamino)propan(o-tolyl)biguanide, di-[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl-tert-octyidiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyidiphenylamines, a mixture of mono- and dialkylatedisopropylisohexyldiphenylamines, mixtures of mono and dialkylatedtert-butyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono and dialkylated tert-butyl-tert-octylphenothiazines, a mixture of mono and dialkylatedtert-octylphenothiazines, N-allylphenothiazine,N,N,N,N-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenediam,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV-absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole,2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole,2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)-benzotriazole,2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole, amixture of2-(3-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3-tert-butyl-5-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazo2-(3-tert-butyl-2′-hydroxy-5-(2-methoxycarbonylethyi)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2-hydroxy-5-(2-methoxycarbonylethyl)phenyl)-benzotriazole,2-(3-tert-butyl-2-hydroxy-5-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3-tert-butyl-5-[2-(2-ethylhexyloxy)carbonylethyl]-2-hydroxyphenyl)benzotriazole,2-(3-dodecyl-2-hydroxy-5-methylphenyl)benzotriazole, and2-(3-tert-butyl-2-hydroxy-5-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3-tert-butyl-5-(2-methoxycarbonylethyl)-2-hydroxyphenyl]benzotriazolewith polyethylene glycol 300;

[R—CH₂CH—COO(CH₂)₃₂ where R=3-tert-butyl-4-hydroxy-5-2H-benzotriazol-2-ylphenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivative.

2.3. Esters of substituted and unsubstituted benzoic acids, for example4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol,benzoylresorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate orisooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate,methyl α-cyano-β-methyl-p-methoxy-cinnamate or butylα-cyano-β-methyl-p-methoxycinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands. 2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethylpiperidyl) sebacate,bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidyl) n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, the condensate ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate,1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate ofN,N′-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1 -(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5 -dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate ofN,N′-bis(2,2,6,6,-tetramethyl-4-piperidyl)-hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine,and also 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]);N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane, thereaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin.

2.7. Oxalamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide,2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide and mixtures of o- andp-methoxy disubstituted oxanilides and mixtures of o- and p-ethoxydisubstituted oxanilides. 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, forexample 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxytridecyloxy-2-hydropropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite,diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,bisisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis-(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylene diphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine fromhydrogenated tallow fatty amines.

6. Nitrones, for example N-benzyl-alpha-phenyl nitron,N-ethyl-alpha-methyl nitron, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl nitrone,N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrones derived fromN,N-dialkylhydroxylamines prepared from hydrogenated tallow fattyamines.

7. Thio synergistic agents, for example dilauryl thiodipropionate ordistearyl thiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, stearate, magnesium behenate, magnesium stearate, sodiumricinoleate, and potassium palmitate, antimony pyrocatecholate or tinpyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talc,metal oxides such as titanium oxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds, such as mono- or polycarboxylic acids and salts thereof, forexample 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid,sodium succinate or sodium benzoate; and polymeric compounds, forexample ionic copolymers (“ionomers”).

12. Fillers and reinforcing agents, for example calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite, wood flour andflours or fibers from other natural products, synthetic fibers.

13. Other additives, for example plasticizers, lubricants, emulsifiers,pigments, rheological additives, catalysts, levelling assistants,optical brighteners, flameproofing agents, antistatic agents and blowingagents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No. 5,175,312,U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643, DE-A-4 316 611, DE-A4316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or3-[4-(2-acetoxyethoxy)phenyl ]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tertbutyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The type and amount of the further stabilizers added is determined bythe type of substrate to be stabilized and on its intended use;frequently, from 0.1 to 5% by weight, based on the polymer to bestabilized, are used.

The novel stabilizers can with particular advantage be employed incompositions in which component (A) is a synthetic organic polymer,especially a thermoplastic polymer, a binder for coatings, for examplepaints, or a photographic material. Examples of suitable thermoplasticpolymers are polyolefins and polymers comprising heteroatoms in the mainchain. Preference is also given to compositions in which component (A)is a thermoplastic polymer comprising nitrogen, oxygen and/or sulphur,especially nitrogen or oxygen, in the main chain.

Also of interest are compositions in which component (A) is apolyolefin, for example polyethylene or polypropylene. `Incorporationinto the organic polymers, for example into the synthetic organic and,in particular, thermoplastic polymers, can be carried out by addition ofthe novel biphenyl-substituted triazine compound and any furtheradditives by the methods conventional in the art. The incorporation canexpediently be made before or during shaping, for example by mixing thepulverulent components or by adding the stabilizer to the melt orsolution of the polymer, or by applying the dissolved or dispersedcompounds to the polymer, with or without subsequent evaporation of thesolvent. Elastomers can also be stabilized as latices. Another way ofincorporating the novel mixtures into polymers comprises adding thembefore or during polymerization of the corresponding monomers or beforecrosslinking.

The novel mixtures can also be added to the plastics to be stabilized inthe form of a master batch which comprises these compounds, for example,in a concentration of from 2.5 to 25% by weight.

The novel mixtures can expediently be incorporated by the followingmethods:

as an emulsion or dispersion (for example to latices or emulsionpolymers)

as a dry mix during mixing of additional components or polymer mixtures

by direct addition to the processing equipment (for example extruders,internal mixers, etc.)

as a solution or melt.

The stabilized polymer compositions obtained in this way can beconverted into shaped articles, for example fibers, films, tapes,sheets, sandwich boards, containers, pipes and other profiles, byconventional methods, for example hot pressing, spinning, extrusion orinjection moulding.

The invention therefore additionally relates to the use of the polymercomposition according to the invention for the production of a shapedarticle.

Use in multilayer systems is also of interest. In this case, a novelpolymer composition having a relatively high content of novelstabilizer, for example, 5-15% by weight, is applied in a thin film(10-100 μm) to a shaped article made from a polymer containing little orno stabilizer of the formula (1) or (1a). Application may be made at thesame time as the shaping of the base structure, for example bycoextrusion. However, application can also be made to the ready-formedbase structure, for example by lamination with a film or by coating witha solution. The outer layer or layers of the finished article have thefunction of a UV filter, which protects the interior of the article fromUV light. The outer layer preferably contains 5-15% by weight, inparticular 5-10% by weight, of at least one compound of the formula (1)or (1a).

The polymers stabilized in this way are notable for high weatheringresistance, especially for high resistance to UV light. This enablesthem to retain their mechanical properties and their colour and glossfor a long time even when used outside.

Likewise of particular interest is the use of the novel mixturescomprising compounds of the formula (1) or (1a) as stabilizers forcoatings, for example for paints. The invention therefore also relatesto those compositions whose component (A) is a film-forming binder forcoatings.

The novel coating composition preferably comprises 0.01-10 parts byweight of (B), in particular 0.05-10 parts by weight of (B), especially0.1-5 parts by weight of (B), per 100 parts by weight of solid binder(A).

Multilayer systems are possible here as well, where the concentration ofthe novel stabilizer (component (B)) in the outer layer can berelatively high, for example from 1 to 15 parts by weight of (B), inparticular 3-10 parts by weight of (B), per 100 parts by weight of solidbinder (A).

The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it prevents delamination, i.e. the flaking-offof the coating from the substrate. This advantage is particularlyimportant in the case of metallic substrates, including multilayersystems on metallic substrates.

The binder (component (A)) can in principle be any binder which iscustomary in industry, for example those described in Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.368-426, VCH, Weinheim 1991. In general, it is a film-forming binderbased on a thermoplastic or thermosetting resin, predominantly on athermosetting resin. Examples thereof are alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) can be a cold-curable or hot-curable binder; the additionof a curing catalyst may be advantageous. Suitable catalysts whichaccelerate curing of the binder are described, for example, in Ullmann'sEncyclopedia of Industrial Chemistry, Vol. A18, p.469, VCHVerlags-gesellschaft, Weinheim 1991.

Preference is given to coating compositions in which component (A) is abinder comprising a functional acrylate resin and a crosslinking agent.

Examples of coating compositions containing specific binders are:

1. paints based on cold- or hot-crosslinkable alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins, ifdesired with addition of a curing catalyst;

2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

3. one-component polyurethane paints based on blocked isocyanates,isocyanurates or polyisocyanates which are deblocked during baking;

4. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

5. two-component paints based on (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methacrylamidoglycolatemethyl ester;

6. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

7. two-component paints based on acrylate resins containing anhydridegroups and on a polyhydroxy or polyamino component;

8. two-component paints based on (poly)oxazolines and acrylate resinscontaining anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

9. two-component paints based on unsaturated polyacrylates andpolymalonates;

10. thermoplastic polyacrylate paints based on thermoplastic acrylateresins or externally crosslinking acrylate resins in combination withetherified melamine resins;

11. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins.

In addition to components (A) and (B), the coating composition accordingto the invention preferably comprises as component (C) a lightstabilizer of the sterically hindered amine and/or2-hydroxyphenyl-2H-benzotriazole type, for example as mentioned in theabove list in sections 2.1 and 2.6. To achieve maximum light stability,it is of particular interest to add sterically hindered amines as setout in the abovementioned list under 2.6. The invention therefore alsorelates to a coating composition which in addition to components (A) and(B) comprises as component (C) a light stabilizer of the stericallyhindered amine type.

This stabilizer is preferably a 2,2,6,6-tetraalkylpiperidine derivativecontaining at least one group of the formula

in which G is hydrogen or methyl, especially hydrogen, and G₁ and G₂ areH or together are ═O.

Component (C) is preferably used in an amount of 0.05-5 parts by weightper 100 parts by weight of the solid binder.

Examples of tetraalkylpiperidine derivatives which can be used ascomponent (C) are given in EP-A-356 677, pages 3-17, sections a) to f).These sections of this EP-A are regarded as part of the presentdescription. It is particular expedient to employ the followingtetraalkylpiperidine derivatives:

bis(2,2,6,6-tetramethylpiperid-4-yl)succinate,

bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,

bis(1,2,2,6,6-pentamethylpiperid-4-yl)sebacate,

di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,

bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)sebacate,

tetra(2,2,6,6-tetramethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,

tetra(1,2,2,6,6-pentamethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,

2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,

8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione,

or a compound of the formulae

 in which m is 5-50.

Apart from components (A), (B) and, if used, (C), the coatingcomposition can also comprise further components, examples beingsolvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents,drying catalysts and/or levelling agents. Examples of possiblecomponents are those described in Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, amino-containing resins and/orphosphines. Examples of organometallic compounds are metal carboxylates,especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metalchelates, especially those of the metals Al, Ti or Zr, or organometalliccompounds such as organotin compounds, for example.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, theoctoates of Co, Zn or Cu, the naphthenates of Mn and Co or thecorresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconiumchelates of acetylacetone, ethyl acetylacetate, salicylaldehyde,salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate,and the alkoxides of these metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltindilaurate or dibutyltin dioctoate.

Examples of amines are, in particular, tertiary amines, for exampletributylamine, triethanolamine, N-methyldiethanolamine,N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine ordiazabicyclooctane (triethylenediamine) and salts thereof. Furtherexamples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride. Amino-containing resins aresimultaneously binder and curing catalyst. Examples thereof areamino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

The novel coating compositions can also be radiation-curable coatingcompositions. In this case, the binder essentially comprises monomericor oligomeric compounds containing ethylenically unsaturated bonds,which after application are cured by actinic radiation, i.e. convertedinto a crosslinked, high molecular weight form. Where the system isUV-curing, it generally contains a photoinitiator as well. Correspondingsystems are described in the abovementioned publication Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

The coating compositions according to the invention can be applied toany desired substrates, for example to metal, wood, plastic or ceramicmaterials. They are preferably used as topcoat in the finishing ofautomobiles. If the topcoat comprises two layers, of which the lowerlayer is pigmented and the upper layer is not pigmented, the novelcoating composition can be used for either the upper or the lower layeror for both layers, but preferably for the upper layer.

The novel coating compositions can be applied to the substrates by thecustomary methods, for example by brushing, spraying, pouring, dippingor electrophoresis; see also Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 491-500.

Depending on the binder system, the coatings can be cured at roomtemperature or by heating. The coatings are preferably cured at 50-150°C., and in the case of powder coatings even at higher temperatures.

The coatings obtained in accordance with the invention have excellentresistance to the damaging effects of light, oxygen and heat; particularmention should be made of the good light stability and weatheringresistance of the coatings thus obtained, for example paints.

The invention therefore also relates to a coating, in particular apaint, which has been stabilized against the damaging effects of light,oxygen and heat by a content of the compound of the formula (1) or (1a)according to the invention. The paint is preferably a topcoat forautomobiles. The invention furthermore relates to a process forstabilizing a coating based on organic polymers against damage by light,oxygen and/or heat, which comprises mixing with the coating compositiona mixture comprising a compound of the formula (1) or (1a), and to theuse of mixtures comprising a compound of the formula (1) or (1a) incoating compositions as stabilizers against damage by light, oxygenand/or heat.

The coating compositions can comprise an organic solvent or solventmixture in which the binder is soluble. The coating composition canotherwise be an aqueous solution or dispersion.

The vehicle can also be a mixture of organic solvent and water. Thecoating composition may be a high-solids paint or can be solvent-free(e.g. a powder coating material).

The pigments can be inorganic, organic or metallic pigments. The novelcoating compositions preferably contain no pigments and are used as aclearcoat.

Likewise preferred is the use of the coating composition as a topcoatfor applications in the automobile industry, especially as a pigmentedor unpigmented topcoat of the paint finish. Its use for underlyingcoats, however, is also possible.

Preference is also given to the use of the novel compound of the formula(1) or (1a) in photographic materials as stabilizer against damage bylight, especially by UV light. The invention therefore also relates to aphotographic material comprising a compound of the formula (1) or (1a).

The compounds according to the invention can be used for photosensitivematerials of all kinds. For example, they can be employed for colourpaper, colour reversal paper, direct-positive colour material, colournegative film, colour positive film, colour reversal film and othermaterials. They are preferably used, inter alia, for photosensitivecolour material which comprises a reversal substrate or which formspositives.

Furthermore, the novel compounds can be combined with other UVabsorbers, especially those which are dispersible in aqueous gelatin,for example with hydroxyphenylbenzotriazoles (cf. for example U.S. Pat.No. 4,853,471, U.S. Pat. No. 4,973,702, U.S. Pat. No. 4,921,966 and U.S.Pat. No. 4,973,701), benzophenones, oxanilides, cyanoacrylates,salicylates, acrylonitriles or thiazolines. In this context it isadvantageous to employ these further, oil-dissolved UV absorbers in thephotographic material in layers other than those comprising the novel UVabsorbers.

In particular, it is possible successfully to stabilize photographicmaterials similar to those described in U.S. Pat. No. 4,518,686.

The invention therefore additionally relates to a photographic materialcomprising, on support, a blue-sensitive, a green-sensitive and/or ared-sensitive silver-halide emulsion layer and, if desired, a protectivelayer, with a layer comprising a UV absorber being arranged above theuppermost silver-halide emulsion layer, wherein the UV absorber is acompound of the formula (1) or (1a).

Preference is additionally given to photographic materials which have alayer comprising a compound of the formula (1) or (1a) above theuppermost silver-halide emulsion layer and/or between the green- andred-sensitive silver-halide emulsion layers.

Furthermore, it may be advantageous for all or some of the said layerswhich can comprise a UV absorber to have a UV absorber mixture and/or afurther UV absorber which is dispersible in aqueous gelatin, but acompound of the formula (1) or (1a) must be present at least in onelayer.

The novel material preferably has gelatin interlayers between thesilver-halide emulsion layers.

Preference is given to photographic materials in which the silver halidein the blue-sensitive, green-sensitive and/or red-sensitive layer issilver chloride bromide comprising at least 90 mol % of silver chloride.

The compounds of the formula (1) or (1a) which are used in accordancewith the invention can be incorporated, alone or together with thecolour coupler and, if used, further additives, into the colourphotographic material by dissolving the compounds beforehand inhigh-boiling organic solvents. It is preferred to use solvents whichboil at higher than 160° C. Typical examples of such solvents are theesters of phthalic acid, phosphoric acid, citric acid, benzoic acid orof fatty acids, and also alkylamides and phenols.

Preferred colour couplers for use in the compositions of the invention,examples of such compounds, further additives such as colour castinhibitors, DIR couplers and further light stabilizers, such as UVabsorbers, phenols, phosphorus(III) compounds, organometallic complexes,hydroquinones and hydroquinone ethers, and more precise details on thestructure of various photographic materials, can be found, for example,in the publications EP-A-531 258 and EP-A-520 938, and in the literaturecited therein.

The novel biphenyl-substituted triazine compounds of the formula (1) or(1a) are suitable for the photochemical stabilization of undyed, dyed orprinted fiber materials comprising, for example, silk, leather, wool,polyamide or polyurethanes, and especially cellulose-containing fibermaterials of all kinds. Examples of such fiber materials are the naturalcellulose fibers, like cotton, linen, jute and hemp, and also viscosestaple fiber and regenerated cellulose.

Preferred textile fiber materials are those of cotton. The novelbiphenyl-substituted triazine compounds are also suitable for thephotochemical stabilization of hydroxyl-containing fibers in blendfabrics, for example blends of cotton with polyester fibers or polyamidefibers. A further preferred area of application relates to the blockingor reduction of the UV radiation which passes through theabove-mentioned textile materials (UV cutting) and the heightened sunprotection which textile materials finished with a novel compound offerto the human skin.

To this end, one or a number of different compounds of the formulae (1)to (4) and (1a) to (4a) are applied to the textile fiber material by oneof the customary dyeing methods, advantageously in a quantity of 0.01 to5% by weight, preferably 0.1-3% by weight and, in particular, from 0.25to 2% by weight, based on the weight of the fiber material.

The novel biphenyl-substituted triazine compounds can be applied to thefiber material in various ways and fixed on the fiber, especially in theform of aqueous dispersions or printing pastes.

The textile fiber materials finished with the novel compounds of theformula (1) or (1a) possess improved protection against photochemicalbreakdown of the fiber and yellowing phenomena, and, in the case of dyedfiber material, are of enhanced (hot) light fastness. Particularemphasis should be drawn to the greatly improved photoprotective effectof the treated textile fiber material and, in particular, the goodprotective effect with respect to short-wave UV-B rays. This ismanifested by the fact that the textile fiber material finished with anovel compound of the formula (1) or (1a) has, relative to untreatedfabric, a greatly increased sun protection factor (SPF).

The sun protection factor is defined as the quotient of the dose of UVradiation which damages protected skin to that which damages unprotectedskin. Accordingly, a sun protection factor is also a measure of theextent to which untreated fiber materials and fiber materials treatedwith a novel compound of the formula (1) or (1a) are permeable to UVradiation. The determination of the sun protection factor of textilefiber materials is explained, for example, in WO 94/04515 or in J. Soc.Cosmet. Chem. 40, 127-133 (1989) and can be carried out analogouslythereto.

The UV absorbers according to the invention are suitable, furthermore,as photoprotective agents in cosmetic preparations.

The invention additionally relates, therefore, to a cosmetic preparationcomprising at least one compound of the formulae (1) and (1a) andcosmetically acceptable carriers or auxiliaries.

The novel cosmetic composition contains from 0.1 to 15% by weight,preferably from 0.5 to 10% by weight, based on the overall weight of thecomposition, of a UV absorber of the formula (1) or (1a) and acosmetically acceptable auxiliary.

The cosmetic composition can be prepared by physically mixing the novelUV absorber with the auxiliary by means of customary methods, forexample by simply stirring together the two materials.

The cosmetic preparation according to the invention can be formulated asa water-in-oil or oil-in-water emulsion, as an oil-in-oil alcohollotion, as a vesicular dispersion of an ionic or nonionic amphiphiliclipid, as a gel, solid stick or as an aerosol formulation.

As a water-in-oil or oil-in-water emulsion, the cosmetically acceptableauxiliary preferably contains from 5 to 50% of an oily phase, from 5 to20% of an emulsifier and from 30 to 90% water. The oil phase mentionedcan comprise any oil which is suitable for cosmetic formulations, forexample one or more hydrocarbon oils, a wax, a natural oil, a siliconeoil, a fatty acid ester or a fatty alcohol. Preferred mono- or polyolsare ethanol, isopropanol, propylene glycol, hexylene glycol, glyceroland sorbitol.

For the cosmetic formulations according to the invention it is possibleto use any conventionally employed emulsifier, for example one or moreethoxylated esters of naturally occurring derivatives, for examplepolyethoxylated esters of hydrogenated castor oil; or a silicone oilemulsifier such as silicone polyol; an unmodified or ethoxylated fattyacid soap; an ethoxylated fatty alcohol; an unmodified or ethoxylatedsorbitan ester; an ethoxylated fatty acid; or an ethoxylated glyceride.

The cosmetic formulation can also comprise further components, forexample emollients, emulsion stabilizers, skin moisteners, tanningaccelerators, thickeners such as xanthan, moisture retention agents suchas glycerol, preservatives, or fragrances and colourants.

The novel cosmetic formulations are notable for good protection of humanskin against the damaging effect of sunlight while at the same timeproviding for reliable tanning of the skin.

The examples which follow describe the invention in more detail withoutrepresenting a limitation. In the examples, parts and percentages are byweight; where an example mentions room temperature, a temperature in therange 20-25° C. is meant. These definitions apply unless statedotherwise in each case.

PREPARATION EXAMPLES OF THE NOVEL COMPOUNDS Example 1

a) 2-(4-Biphenyl)-4H-1,3-benzoxazin-4-one

15.07 g of salicyl amide are dissolved in 30 ml of xylene (+1 ml ofpyridine) at boiling, and 21.7 g of biphenyl-4-carbonyl chloridedissolved in 100 ml of xylene are added over the course of 2.5 hours at70° C. The mixture is stirred at a bath temperature of 180° C. for about4 hours and then evaporated to dryness, to leave 35.3 g of an oilyresidue of the compound of the formula

b) 2-(2-Hydroxyphenyl)-4-phenyl-6-(1-biphenyl)-1,3,5-triazine

The oily residue of the compound of the formula (101) is dissolved at40° C. in 400 ml of methylcellosolve, and then 45.7 g of a 38% solutionof benzamidine hydrochloride in methanol are added, followed by 19.6 gof a 30% sodium hydroxide solution. The mixture is subsequently stirredat 90° C. for 4 hours and filtered, to give 19.7 g of an almostcolourless, crystalline product of the formula

Yield: 49% of theory; m.p.: 252-259° C.; Elemental analysis forC₂₇H₁₉N₃O:

C H N O calculated: 80.78% 4.77% 10.47% 3.99% found: 80.74% 4.87% 10.50%3.93%

Example 2

16.15 g of 2-phenyl-4H-1,3-benzoxazin-4-one (prepared analogously toHelv. Chim. Acta 55, 1566-1599 (1972)) are dissolved in 100 ml ofmethanol, and 12.0 g of 4-biphenylamidine hydrochloride are added. Then13.5 g of a 40% sodium methylate solution are added and the mixture isstirred at a bath temperature of 70° C. for 2 hours. Filtration gives16.75 g of the compound of the formula (102).

Yield: 83.5%.

Example 3

The procedure described in Example 1b) is repeated but using 24.4 g ofthe compound of the formula (101) and 17 g of 4-biphenylamidinehydrochloride instead of benzamidine hydrochloride. Working up gives21.6 g of the compound of the formula

Yield: 61.5% of theory; m.p.: 262-265° C.; Elemental analysis forC₃₃H₂₃N₃O×0.5 H₂O:

C H N calculated: 81.46% 4.98% 8.63% found: 81.35% 5.08% 8.51%

Example 4

4.65 g of biphenylamidine hydrochloride are dissolved in 8.9 ml ofdimethylacetamide. Then, in succession, 3.65 ml of a 30% methanolicsodium methylate solution, 2.97 g of methyl salicylate and 10.6 ml ofcyclohexane are added, the mixture is heated to a bath temperature of90° C. over the course of 30 minutes, and it is stirred at thistemperature for 20 hours. It is then cooled to 5° C. and filtered, togive 1.05 g of a pale yellowish product of the formula (103) (seeExample 3).

Yield: 22% of theory.

Example 5

a) 4.65 g of 4-biphenylamidine hydrochloride are suspended in 6.7 ml ofmethanol. Then, in succession, 3.6 g of 30% sodium methylate solutionand 1.22 g of salicylaldehyde are added.

The mixture is stirred at 60-64° C. for 6 hours and filtered, to give,after washing with water and methanol, 4.4 g of a pale beige product ofthe formula

C H N O calculated: 82.65% 5.25% 8.76% 3.34 found: 81.40% 5.19% 8.61%3.85

b) 4.8 g of the compound of the formula (104) are dissolved in 35 ml ofdimethylformamide, and 3.83 ml of a 40% aqueous sodium bisulphitesolution are added. The mixture is stirred at 48° C. for 6 hours. It isthen filtered at room temperature and the filter product is dried, togive 4.62 g of a pale yellowish beige product of the formula (103) (seeExample 3).

Yield: 96.3% of theory.

Example 6 (Prior Art)

4.6 g of resorcinol are dissolved in 40 ml of nitrobenzene, and then3.82 g of 2-(4-biphenyl)-4,6 dichlo-1,3,5-triazine are added at roomtemperature. 3.37 g of anhydrous aluminium trichloride are thenintroduced, with ice cooling, so that the temperature does not riseabove 20° C. The mixture is subsequently heated to a bath temperature of92° C. and stirred at this temperature for 2 hours. It is cooled andpoured into a mixture of 100 ml of H₂O, 90 g of ice and 10 ml of conc.HCl. Subsequent steam distillation and working up give 7.38 g of a paleyellow-orange powder of the formula

Yield: 85.2% of theory; Elemental analysis for C₂₇H₁₉N₃O₄×1.33 H₂O:

C H N H₂O calculated: 68.5%  4.61% 8.88% 5.06% found: 68.37% 4.58% 8.79%5.05%

Example 7

2 g of the compound of the formula (105) prepared in Example 6 aredissolved in 30 ml of dimethyl methanephosphonate together with 3 g ofsodium carbonate, and the solution is stirred at 150° C. for 2 hours.After cooling, it is diluted with 500 ml of ethanol and filtered to give1.85 g of a pale beige product of the formula

Yield: 86% of theory;

Elemental analysis for C₃₀H₂₅N₃O₄:

C H N calculated: 73.31% 5.13% 8.55% found: 73.27% 5.15% 8.48%

Example 8

The procedure described in Example 2 is repeated but using2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one instead of2-phenyl-4H-1,3-benzoxazin-4-one. Working up gives the compound of theformula

Yield: 81% of theory;

m.p.: 289-290° C.; Elemental analysis for C₂₇H₁₉N₃O₂:

C H N calculated: 77.68% 4.59% 10.07% found: 77.67% 4.64% 10.04%

Example 9

The procedure described in Example 7 is repeated but using the compoundof the formula (107) instead of the compound of the formula (105), togive the compound of the formula

Yield: 100%; m.p.: 228-229° C.; Elemental analysis for C₂₈H₂₁N₃O₂×1.5H₂O:

C H N calculated: 73.34% 5.27% 9.16% found: 73.4%  4.5%  9.1% 

Example 10

The procedure described in Example 2 is repeated but using2-(4-methoxyphenyl)-4H-1,3-benzoxazin-4-one instead of2-phenyl-4H-1,3-benzoxazin-4-one. Working up gives the pale beigecompound of the formula

Elemental analysis for C₂₈H₂₁N₃O₂:

C H N calculated: 77.94% 4.91% 9.74% found: 77.84% 4.94% 9.68%

Example 11

a) The procedure described in Example 1a) is repeated, but using4-methoxysalicylamide instead of salicylamide. The residue correspondsto the compound of the formula

b) The compound of the formula (110) is processed further withoutpurification as described in Example 2, using 4-biphenylamidinehydrochloride instead of benzamidine hydrochloride. This gives thecompound of the formula

Yield: 34% of theory; Elemental analysis for C₃₄H₂₅N₃O₂:

C H N calculated: 80.45% 4.96% 8.28% found: 80.58% 4.95% 8.18%

Example 12

The procedure described in Example 2 is repeated but using2-(4-cyanophenyl)-4H-1,3-benzoxazin-4-one instead of2-phenyl-4H-1,3-benzoxazin-4-one. Working up gives the compound of theformula

Yield: 31% of theory; Elemental analysis for C₂₈H₁₈N₄O×0.08 H₂O:

C H N H₂O calculated: 78.59% 4.28% 13.09% 0.34% found: 78.57% 4.33%12.91% 0.34%

Example 13

The procedure described in Example 2 is repeated, but using instead of2-phenyl-4H-1,3-benzoxazin-4-one the compound of the formula

Working up gives the compound of the formula

Yield: 72.6% of theory; m.p.: 240-242° C.; Elemental analysis forC₂₈H₁₉N₃O₃:

C H N O calculated: 75.49% 4.3%  9.43% 10.77% found: 75.45% 4.36% 9.36%10.83%

Example 14

3.6 g (0.147 mol) of magnesium are suspended in 50 ml of THF, and asolution of 34.3 g (0.147 mol) of 4-bromobiphenyl in 50 ml of THF isadded dropwise. The mixture is then heated at reflux for 2 hours. Thismixture is added dropwise to a solution of 9.2 g (0.05 mol) of cyanuricchloride in 50 ml of THF (50° C.). After 4 hours, 100 ml of toluene areadded and the mixture is poured into 50 ml of 12% HCl, during which aproduct precipitates. The mixture is filtered and the filter residue iswashed with water. After drying, it is chromatographed over silica gelto give 8.3 g of the product of the formula

Yield: 35% of theory; Elemental analysis for C₂₇H₁₈N₃Cl:

C H N Cl: calculated: 77.23% 4.32% 10.01% 8.44% found: 77.10% 4.52% 9.95% 8.13%

Example 15

17.6 g (0.042 mol) of 2-chloro-4,6-bisbiphenyl-1,3,5-triazine (compoundof the formula 114) are suspended in 100 ml of toluene. AlCl₃ is addedas catalyst, and the mixture is heated to 100° C. 4.7 g (0.042 mol) ofresorcinol are added in portions. The mixture is then heated at refluxfor 12 hours. The reaction mixture is poured into an ice-water mixture,during which a product precipitates. The mixture is filtered and thefilter residue is washed with water, to give 14.5 g of a product of theformula

Yield: 70%; Elemental analysis for C₃₃H₂₃N₃O₂:

C H N calculated: 80.31% 4.70% 8.51% found: 80.26% 4.55% 8.23%

Example 16

9.9 g (0.02 mol) of the compound of the formula (115) (see Example 15)and 3 g (0.022 mol) of potassium carbonate are suspended in 50 ml ofethylcellosolve. The mixture is heated to 110° C., and 3.6 g (0.022 mol)of 1-bromohexane are added dropwise. The mixture is stirred at 110° C.for 21 hours. On cooling the mixture, a product is precipitated. Themixture is filtered and the filter residue is washed with water, to givea product of the formula

Yield: 69%; m.p.: 176-178° C.; Elemental analysis for C₃₉H₃₅N₃O₂:

C H N calculated: 81.08% 6.11% 7.27% found: 80.91% 6.28% 7.14%

Example 17

8.5 g (0.0172 mol) of the compound of formula (115) (see Example 15),3.4 g (0.025 mol) of butyl glycidyl ether and 0.5 g (0.0014 mol) ofethyltriphenylphosphonium bromide are suspended in 200 ml of xylene. Themixture is heated at reflux for 17 hours. The xylene is evaporated offand the residue is recrystallized, to give 6.5 g of the compound of theformula

Yield: 61%; m.p.: 156-158° C.;

Elemental analysis for C₄₀H₃₇N₃O₄:

C H N calculated: 77.02% 5.98% 6.74% found: 76.78% 5.97% 6.72%

Example 18

23.2 g (0.047 mol) of the compound of the formula (115) (see Example 15)and 7.2 g (0.052 mol) of potassium carbonate are suspended in 100 ml ofethylcellosolve. The mixture is heated to 110° C., and 10 g (0.052 mol)of 1-bromooctane are added dropwise. The mixture is stirred at 130° C.for 3 hours. On cooling the mixture, a product is precipitated. Themixture is filtered and the filter residue is washed with water, to give13.3 g of the compound of the formula

Yield: 47%; m.p.: 158-160° C.,

Example 19

8.1 g (0.0165 mol) of the compound of formula (115) (see Example 15),6.8 g (0.028 mol) of a C₁₂/C₁₃-alkyl glycidyl ether isomer mixture and0.6 g (0.0016 mol) of ethyltriphenylphosphonium bromide are suspended in150 ml of xylene. The mixture is heated at reflux for 23 hours. Thesolvent is evaporated off and the residue is chromatographed over silicagel, to give 9.8 g of the compound of the formula

Yield: 81%; m.p.: 80-88° C.

Example 20

22.2 g (0.045 mol) of2-(2,4-dihydroxyphenyl)-4,6-bisbiphenyl-1,3,5-triazine, corresponding tothe formula (115), and 6.8 g (0.05 mol) of potassium carbonate aresuspended in 150 ml of ethylcellosolve. The mixture is heated to 110°C., and 10.9 g (0.05 mol) of 1-bromodecane are added dropwise. Themixture is stirred at 110° C. for 12 hours. On cooling the mixture, aproduct is precipitated. The mixture is filtered and the residue isrecrystallized to give 8 g of a compound of the formula

(Yield 28%, m.p.: 154-157° C.);

Elemental analysis (%)

C H N calculated: 81.48 6.84 6.63 found: 81.41 6.74 6.62

Example 21

10 g (0.016 mol) of2-(2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl)-4,6-bisbiphenyl-1,3,5-triazine,corresponding to the formula (117), in 100 ml of a xylene isomer mixtureare heated to 120° C. Then 4.7 g (0.0352 mol) of caproyl chloride areadded dropwise. 5 drops of pyridine are added as well, and the mixtureis stirred at 120° C. for 12 hours. The mixture is cooled and theorganic phase is washed with water and then dried over MgSO₄. Afterevaporation of the solvent, the residue is chromatographed over silicagel to give 8.6 g of a compound of the formula

as a resin (Yield 74%). Elemental analysis (%)

C H N calculated 76.54 6.56 5.82 found: 76.27 6.66 5.30

Example 22

2.3 g (0.025 mol) of the compound of the formula (115) and 5.18 g(0.0375 mol) of potassium carbonate is suspended in 150 ml ofethylcellosolve, the mixture is heated to 110° C., and 9.35 g (0.0375mol) of 1-bromododecane are added. The mixture is stirred at 110° C. for12 hours. On cooling the mixture, a product is precipitated. The mixtureis filtered and the residue is recrystallized to give 6.3 g of acompound of the formula

(Yield 38%, m.p.: 143-146° C.); Elemental analysis (%)

C H N calculated: 81.66 7.16 6.35 found: 81.66 7.33 6.21

Example 23

The benzoxazinone of the formula (101) is reacted as described inExample 1 with the following substituted benzamidines:

a. with 3-amidobenzamide of the formula

to give the compound of the formula

m.p.: 297-298° C; Elemental analysis for C₂₈H₂₀N₄O₂:

C H N O calculated: 75.66 4.54 12.6 7.2 found: 75.65 4.65 12.57 7.13

b) with methyl 4-amidobenzoate of the formula

to give the compound of the formula

m.p.: 198-200° C. Elemental analysis for C₂₉H₂₁N₃O₃:

C H N O calculated: 75.80 4.61 9.14 10.45 found: 75.81 4.88 9.02 10.29

Example 24

9.4 g (0.019 Mol)2-(2,4-dihydroxyphenyl)-4,6-bis-(4-biphenyl)-1,3,5-triazine aresuspended in 100 ml of ethyl methyl ketone, 2.6 g (0.019 Mol) potassiumcarbonate and 6.1 g (0.021 Mol) 2-bromopentane acid octylester (octylisomeric mixture). The mixture is stirred for 12 hours at 100° C., thenfiltered and reduced. The residue is chromatographed over silica gel, togive 6.3 g (47%) of a waxy product of the formula

¹H-NMR-spectrum is in accordance with the formula. Elemental analysisfor C₄₅H₃₇N₃O₄:

C H N calculated: 78.27 6.71 5.95 found: 79.25 7.18 5.18

Using 2-bromopropane acid octyl ester (octyl isomeric mixture) insteadof the above bromoalkyl ester in the same procedure gives2-(2-hydroxy-4-{1-octyloxycarbonylethyloxy}-phenyl)-4,6-bis-(4-biphenyly)-1,3,5-triazine.

Use Examples Example 25 Stabilization of a 2-Coat Metallic Finish

The compounds to be tested are dissolved in 20-30 g of Solvesso® 150 andtested in a clearcoat having the following composition:

Synthacryl ® SC 303¹ 27.51 Synthacryl ® SC 370² 23.34 Maprenal ® 650³27.29 Butyl acetate/Butanol (37/8) 4.33 Isobutanol 4.87 Solvesso ® 150⁴2.72 Crystal Oil K-30 8.74 Levelling assistant Baysilon ® MA⁵ 1.20100.00 g ¹Acrylate resin, Hoechst AG; 65% solution in xylene/butanol26:9 ²Acrylate resin, Hoechst AG; 75% solution in Solvesso ® 100³Melamine resin, Hoechst AG; 55% solution in isobutanol ⁴aromatichydrocarbon mixture, boiling range 182-203° C. (Solvesso ® 150) or161-178° C. (Solvesso ® 100); manufacturer: Esso ⁵1% in Solvesso ® 150;manufacturer: Bayer AG

1.5% of the compounds to be tested are added to the clearcoat, based onthe solids content of the varnish. Some further varnish samples areprepared which, in addition to the novel compounds, contain 1% of thecompound of the formula

based on the solids content of the coating composition. For comparison,a clearcoat containing no light stabilizer is used.

The clearcoat is diluted with Solvesso® 100 to spray viscosity and isapplied by spraying to a prepared aluminium panel (Uniprime Epoxy,silver-metallic basecoat) which is baked at 130° C., for 30 minutes, togive a dry film thickness of 40-50 μm of clearcoat.

The samples are subjected to weathering as follows:

UVCON® weathering instrument from Atlas Corporation (UVB-313 lamps) witha cycle of 8 h radiation at 70° C. and 4 h condensation at 50° C.

QUV® weathering instrument from Q-Panel (UVA-340 lamps—high intensity)with a cycle of 8 h radiation at 70° C. and 4 h condensation at 50° C.

The surface gloss (20° gloss, DIN 67530) of the samples is measured.

Compounds used:

Compound of the formula (116) (Example 16)

Compound of the formula (119) (Example 19)

Compound of the formula (121) (Example 21)

Results:

TABLE 1 20° gloss after 0, 1200 h weathering in the UVCON (UVB-313)bisbiphenyltriazines alone 0 1200 unstabilized 87 70 compound of theformula (116) 88 84 1.5% of the compound of the formula (119) 85 87 1.5%of the compound of the formula (121) 87 86

TABLE 2 20° gloss after 0, 1200 h weathering in the UVCON (UVB-313);combination of bisbiphenyltriazines with Tinuvin 292 (HALS) 0 1200unstabilized 87 70 1% of the compound of the formula (125) 87 76 1.5% ofthe compound of the formula (116)/ 87 82 1% of the compound of theformula (125) 1.5% of the compound of the formula (119)/ 87 84 1% of thecompound of the formula (125) 1.5% of the compound of the formula (121)/87 86 1% of the compound of the formula (125)

TABLE 3 20° gloss after 0, 1200 h weathering in the QUV-A (highintensity) bisbiphenyltriazines alone 0 1200 unstabilized 87 60 1.5% ofthe compound of the formula (116) 88 89 1.5% of the compound of theformula (119) 85 88 1.5% of the compound of the formula (121) 87 90

TABLE 4 20° gloss after 0, 1200 h weathering in the QUV-A (highintensity) Combination of bisbiphenyltriazines with Tinuvin 292 (HALS) 01200 unstabilized 87 60 1% of the compound of the formula (125) 87 841.5% of the compound of the formula (116)/ 87 90 1% of the compound ofthe formula (125) 1.5% of the compound of the formula (119)/ 87 90 1% ofthe compound of the formula (125) 1.5% of the compound of the formula(121)/ 87 90 1% of the compound of the formula (125)

The results listed in Tables 1 to 4 show that the samples stabilized inaccordance with the invention have better weathering stability (glossretention) than the unstabilized comparison sample.

Example 26 Use in Polycarbonate

10 g of polycarbonate powder (Lexan 115) are dissolved with stirring in50 g of methylene chloride at room temperature, a process which takesseveral hours. Also added is 0.2 g of UV absorber, corresponding to a 2%concentration of additive. These solutions are used to cast films with athickness of 20 μm.

The films are exposed in an Atlas Weatherometer Cl 65 at a black paneltemperature of 63° C. and a relative humidity of 60%. The discolourationof the samples is checked at regular intervals by measuring theYellowness Index (YI, method DIN 6167). Table 5 shows the exposure timeuntil a Yellowness Index of 7 is obtained.

The films are then exposed further until they become brittle, which isshown by the development of cracks in the films. The duration ofexposure until embrittlement occurs is likewise given in Table 5.

TABLE 5 Exposure time (h) until Yellowness Index (YI) of 7 is reachedand until embrittlement. Exposure time (h) until UV absorber YI = 7Embrittlement none 990 1000 2% of the compound of the formula (126) 13204057 2% of the compound of the formula (102) 2480 6060

The following UV absorbers are employed:

a) compound of the formula

b) compound of the formula (102) from Example 1b)

Example 27

Polycarbonate powder is mixed with 0.3% of the UV absorber of theformula (102) and the mixture is processed to give granules in atwin-screw extruder at a melt temperature of 275° C. at a speed of 25rpm.

The granules are injection-moulded (240/300° C./75 bar) to give sheetsmeasuring 67×43×2 mm. The sheets are exposed in an Atlas WeatherometerCl 65, as described in Example 25. Table 6 shows the exposure time untila Yellowness Index of 20 is obtained (YI, measured in accordance withDIN 6167).

TABLE 6 Exposure time (h) until a Yellowness Index (YI) of 10; 15; 20;is reached Exposure time (h) until YI = UV absorber 10 15 20 none  375 695  940 compound of the formula (102) 1160 1600 3950

Example 28

10 g of polycarbonate powder (Lexan 115) are dissolved with stirring in50 g of methylene chloride at room temperature, a process which takesseveral hours. Also added is 0.2 g of the UV absorber of formula (116),corresponding to a 2% concentration of additive.

These solutions are used to cast films with a thickness of 20 μm.

The films are exposed in an Atlas Weatherometer Cl 65 at a black paneltemperature of 63° C. and a relative humidity of 60%. The discolourationof the samples is checked at regular intervals by measuring theYellowness Index (YI, method DIN 6167). Table 7 gives the difference inthe Yellowness Index (ΔYI) between the value after 500 and 1000 hoursand the initial value.

TABLE 7 ΔYI after exposure UV absorber 500 h 1000 h none 2.2 7.1 2% ofthe compound of the formula (116) 0.5 1.1

Example 28 Cosmetic Use

Suspension of the compound of formula (120)

Biphenyl-triazin-UV-absorber of the formula (120) 3 g C₈—C₁₂-fattyalcohol polyglucoside 2.4 g sodium chloride 1 g Xanthan gum 0.5 gBronopol 0.1 g deionized water 93 g

Preparation of the Formulation

40 g of the UV absorber, 20 g of the fatty alcohol polyglucoside and 40g water are mixed together und milled with a ball mill (Drais), so thatthe diameter of the milled particles becomes smaller than 1 μm. Startingform this paste the other components of the above dispensing are admixedaccordingly.

The measured sun protection factors (SPF) and photo stabilities can beseen from Table 8.

TABLE 10 sun protection photo concentration factor *) stability **) [h]compound of the 3% 19.7 1400 h formula (120) *) by Diffey and Robson **)as half-life period of the photochemical decomposition in D65-light inethanolic solution.

The results show that the effective substances have a high photostability and that a high sun protection factor can be obtained with alow concentration.

What is claimed is:
 1. A biphenyl-substituted triazine compound of theformula

in which R₁ is hydrogen; C₁-C₂₄alkyl or C₅-C₁₂cycloalkyl; or R₁ isC₁-C₂₄alkyl or C₅-C₁₂cycloalkyl, each of which is substituted byhalogen, —R₄, —OR₅, —N((R₅)₂, ═NR₅, ═O, —CON(R₅)₂, —COR₅, —COOR₅,—OCOR₅, —OCON(R₅)₂, —CN, —NO₂, —SR₅,—SOR₅, —SO₂R₅, —P(O)(OR₅)₂, amorpholinyl, piperidyl, 2,2,6,6-tetramethylpiperidyl, piperazinyl orN-methylpiperazinyl-group, or combinations thereof; and/or R₁ isC₁-C₂₄alkyl or C₅-C₁₂cycloalkyl which is interrupted by 1 to 6phenylene, —O—, —NR₅—, —CONR₅—, —COO—, —OCO—, —CH(R₅)—, —C(R₅)₂— or —CO—groups or combinations thereof; C₂-C₂₄alkenyl; halogen; —SR₃, SOR₃;SO₂R₃; —SO₃H; —SO₃M; or a radical of the formula

R₃ is C₁-C₂₀alkyl; C₃-C₁₈alkenyl; C₅-C₁₂cycloalkyl; C₇-C₁₅phenylalkyl;or C₆-C₁₂aryl which is unsubstituted or substituted by 1 to 3 C₁-C₄alkylgroups; R₄ is C₆-C₁₂aryl; or C₆-C₁₂aryl which is substituted by halogen,C₁-C₈alkyl, C₁-C₈alkoxy or combinations thereof; C₅-C₁₂cycloalkyl;C₇-C₁₅phenylalkyl; or C₇-C₁₅phenylalkyl which is substituted in thephenyl ring by 1 to 3 halogen atoms, C₁-C₈alkyl, C₁-C₈alkoxy orcombinations thereof or C₂-C₈alkenyl; R₅ is R₄; hydrogen; C₁-C₂₄alkyl;or a radical of the formula

T is hydrogen; C₁-C₈alkyl; C₂-C₈alkyl which is substituted by hydroxylor acyloxy; oxyl; hydroxyl; —CH₂CN;, C₁-C₁₈alkoxy; C₅-C₁₂cycloalkoxy;C₃-C₆alkenyl; C₇-C₉phenylalkyl; C₇-C₉phenylalkyl which is substitutedone, two or three times in the phenyl ring by C₁-C₄alkyl; or aliphaticC₁-C₈alkanoyl; R₆ to R₁₅ independently of one another are hydrogen;hydroxyl; —C≡N; C₁-C₂₀alkyl; C₁-C₂₀alkoxy; phenyl-C₁-C₂₀alkoxy;C₇-C₂₀phenylalkyl; C₄-C₁₂cycloalkyl; C₄-C₁₂cycloalkoxy; halogen;halo-C₁-C₅alkyl; carboxyl; acylamino; acyloxy; C₁-C₁₂alkoxycarbonyl;aminocarbonyl; —O—Y; or O—Z; or R₁₁ and R₁₂, together with the phenylradical, form a cyclic radical containing 2 to 4 carbon atoms which isinterrupted by oxygen or —NR₅—; M is alkali metal; p 1 or 2; q is 0; ifp is 1, X, Y and Z independently of one another are hydrogen;C₃-C₅₀alkyl which is interrupted by oxygen and/or substituted by R₂ orOR₂; ((CH₂)_(m)—CH₂—O—)_(n)—R₂; —(CH₂—CH((CH₂)_(m)—R₂)—O—)_(n)—R′₂;—(CH((CH₂)_(m)—R₂)—CH₂—O—)_(n)—R′₂; —(CH₂)_(n)—R₂;

 C₄-C₁₂cycloalkyl which is substituted by R₂; —OR₂-substitutedC₄-C₁₂cycloalkyl; —CH((CH₂)_(n)—R₂)—CO—O—(CH₂)_(m)—R′₂;—CH((CH₂)_(n)—R₂)—CO—(NR′)—(CH₂)_(m)—R′₂; —CO—(CH₂)_(n)—R₂;—CO—O—(CH₂)_(n)—R₂, —CH₂—CH(—O(CO)—R₂)—R′₂; —CO—NR′—(CH₂)_(n)—R₂;C₆-C₁₂aryl; allyl; C₄-C₂₀alkenyl; C₄-C₂₀alkenyl which is interrupted byoxygen; C₄-C₁₂cycloalkenyl; C₄-C₁₂cycloalkenyl which is interrupted byoxygen; or C₃-C₂₀alkynyl; R₂ and R′₂, independently of one another areR_(x) if attached to a carbon atom and are R_(y) if attached to an atomother than carbon; n 0 to 20; m 0 to 20; and, if p is 2, Y and Z,independently of one another are as defined for when p is 1; and X isC₂-C₁₂alkylene; —CO—(C₂-C₁₂alkylene)—CO—; CO-phenylene-CO—;CO-biphenylene-CO—; CO—O—(C₂-C₁₂alkylene)—O—CO—; —CO—O-phenylene-O—CO—;—CO—O-biphenylene-O—CO—; —CO—NR′—(C₂-C₁₂alkylene)—NR′—CO—;—CO—NR′-phenylene-NR′—CO—; —CO—NR′-biphenylene-NR′—CO—;—CH₂—CH(OH)—CH₂—; —CH₂—CH(OR₂)—CH₂—;—CH₂—CH(OH)—CH₂—O—D—O—CH₂—CH(OH)—CH₂;—CH₂—CH(OR₂)—CH₂—O—D—O—CH₂—CH(OR₂)—CH₂—; D is C₂-C₁₂alkylene;C₄-C₅₀alkylene which is interrupted by oxygen; phenylene; biphenylene orphenylene-E-phenylene; E is —O—; —S—; —SO₂—; —CH₂—; —CO—; or —C(CH₃)₂—;R_(x) is hydrogen; hydroxyl; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl;C₁-C₂₀alkoxy; C₄-C₁₂cycloalkoxy; C₄-C₁₂cycloalkyl or C₄-C₁₂cycloalkoxyeach of which is interrupted by oxygen; C₆-C₁₂aryl; pyridyl;pyrimidinyl; triazinyl; pyrrolyl; furyl; thiophenyl; quinolyl; —OR_(z);NHR_(z); R_(z); CONR′R″; C₂-C₂₀alkenyl; C₄-C₁₂cycloalkenyl;C₄-C₁₂cycloalkenyl which is interrupted by oxygen; C₃-C₂₀alkynyl; or isany of the above alkyl, cycloalkyl, cycloalkenyl, alkoxy, cycloalkoxy,oxygen interrupted cycloalkyl or cycloalkenyl or cycloalkoxy, aryl,heteroaryl, alkenyl or alkynyl which is substituted by hydroxyl, —NH₂,—NHR₅, —NR₅R′₅, where R′₅ is defined as R₅ above, halogen, C₁-C₂₀alkyl,C₁-C₂₀alkoxy, C₄-C₁₂cycloalkyl, C₄-C₁₂cycloalkoxy, C₂-C₂₀alkenyl,C₄-C₁₂cycloalkyl, C₃-C₂₀alkynyl, C₆-C₁₂aryl, C₂-C₁₈acylamino,C₂-C₁₈acyloxy, carboxyl, acryloxy, acrylamino, methacryloxy,methacrylamino,

R_(y) is hydrogen; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl; C₄-C₁₂cycloalkyl whichis interrupted by oxygen; C₆-C₁₂aryl; pyridyl; pyrimidinyl; triazinyl;pyrrolyl; furyl; thiophenyl; quinolyl; R_(z); C₂-C₂₀alkenyl;C₄-C₁₂cycloalkenyl; C₄-C₁₂-cycloalkenyl which is interrupted by oxygen;or C₃-C₂₀alkynyl; or is any of the above alkyl, cycloalkyl, aryl,hetero-aryl, alkenyl, cycloalkenyl or alkynyl, which is substituted byhydroxyl, —NH₂, —NHR₅, —NR₅R′₅, where R′₅ is defined as R₅ above,halogen, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, C₄-C₁₂cycloalkyl, C₄-C₁₂cycloalkoxy,C₂-C₂₀alkenyl, C₄-C₁₂cycloalkyl, C₃-C₂₀alkynyl, C₆-C₁₂aryl,C₂-C₁₈acylamino, C₂-C₁₈acyloxy, carboxyl, acryloxy, acrylamino,methacryloxy, methacrylamino,

R_(z) is —COR′; —COOR′; —CONR′R″; —CO—CH═CH₂; —CO—C(CH₃)═CH₂; R′ and R″independently of one another are hydrogen; C₁-C₂₀alkyl; C₄-C₅₀alkylwhich is interrupted by oxygen; C₄-C₁₂cycloalkyl; C₄-C₁₂cycloalkyl whichis interrupted by oxygen; C₂-C₂₀alkenyl; C₄-C₂₀alkenyl which isinterrupted by oxygen; or C₆-C₁₂aryl; or are any of the above alkyl,O-interrupted alkyl, cycloalkyl, O-interrupted cycloalkyl, alkenyl,O-interrupted alkenyl, aryl, which is substituted by hydroxyl, —NH₂,—NHR₅, —NR₅R′₅, where R′₅ is defined as R₅ above, halogen, C₁-C₂₀alkyl,C₁-C₂₀alkoxy, C₄-C₁₂cycloalkyl, C₄-C₁₂cycloalkoxy, C₂-C₂₀alkenyl,C₄-C₁₂cycloalkyl, C₃-C₂₀alkynyl, C₆-C₁₂aryl, C₂-C₁₈acylamino,C₂-C₁₈acyloxy, carboxyl, acryloxy, acrylamino, methacryloxy,

 and with the proviso that the compound2-(2-hydroxyphenyl)-4-phenyl-6-(1-biphenyl)-1,3,5-triazine is notincluded; and with the proviso that R₁₂ and R₁₃ are not hydroxyl orallyloxy.
 2. A triazine compound according to claim 1 of formula (1) or(1a)

in which R₁ is hydrogen; C₁-C₂₄alkyl or C₅-C₁₂cycloalkyl; or R₁ isC₁-C₂₄alkyl or C₅-C₁₂cycloalkyl, each of which is substituted byhalogen, —R₄, —OR₅, —N((R₅)₂, ═NR₅, ═O, —CON(R₅)₂, —COR₅, —COOR₅,—OCOR₅, —OCON(R₅)₂, —CN, —NO₂, —SR₅, —SOR₅, —SO₂R₅, —P(O)(OR₅)₂, amorpholinyl, piperidyl, 2,2,6,6-tetramethylpiperidyl, piperazinyl orN-methylpiperazinyl-group, or combinations thereof; and/or R₁ isC₁-C₂₄alkyl or C₅-C₁₂cycloalkyl which is interrupted by 1 to 6phenylene, —O—, —NR₅—, —CONR₅—, —COO—, —OCO—, —CH(R₅)—, —C(R₅)₂— or —CO—groups or combinations thereof; C₂-C₂₄alkenyl; halogen; —SR₃, SOR₃;SO₂R₃; —SO₃H; —SO₃M; or a radical of the formula

R₃ is C₁-C₂₀alkyl; C₃-C₁₈alkenyl; C₅-C₁₂cycloalkyl; C₇-C₁₅phenylalkyl;C₆-C₁₂aryl; or C₆-C₁₂aryl which is substituted by 1 to 3 C₁-C₄alkylgroups; R₄ is C₆-C₁₂aryl; or C₆-C₁₂aryl which is substituted by 1 to 3halogen atoms, C₁-C₈alkyl or C₁-C₈alkoxy or combinations thereof;C₅-C₁₂cycloalkyl; C₇-C₁₅phenylalkyl; or C₇-C₁₅phenylalkyl which issubstituted in the phenyl ring by 1 to 3 halogen atoms, C₁-C₈alkyl,C₁-C₈alkoxy or combinations thereof or C₂-C₈alkenyl; R₅ is R₄; hydrogen;C₁-C₂₄alkyl; or a radical of the formula

T is hydrogen; C₁-C₈alkyl; C₂-C₈ alkyl which is substituted by hydroxylor by acyloxy; oxyl; hydroxyl; —CH₂CN; C₁-C₁₈alkoxy; C₅-C₁₂cycloalkoxy;C₃-C₆alkenyl; C₇-C₉phenylalkyl; C₇-C₉phenylalkyl which is substitutedone, two or three times in the phenyl ring by C₁-C₄alkyl; or T isaliphatic C₁-C₈alkanoyl; R₆ to R₁₅ independently of one another arehydrogen; hydroxyl; —C≡N; C₁-C₂₀alkyl; C₁-C₂₀alkoxy; C₇-C₂₀phenylalkyl;C₄-C₁₂cycloalkyl; C₄-C₁₂cycloalkoxy; halogen; halo-C₁-C₅alkyl; carboxyl;acylamino; acyloxy; C₁-C₁₂alkoxycarbonyl; aminocarbonyl; —O—Y; or O—Z;or R₁₁ and R₁₂, together with the phenyl radical, form a cyclic radicalcontaining 2 to 4 carbon atoms which is interrupted by oxygen or —NR₅—;M is alkali metal; p 1; q is 0; X, Y and Z independently of one anotherare hydrogen, ((CH₂)_(m)—CH₂—O—)_(n)—R₂;—CH((CH₂)_(n)—R₂)—CO—O—(CH₂)_(m)—R′₂;—(CH₂—CH((CH₂)_(m)—R₂)—O—)_(n)—R′₂; —(CH((CH₂)_(m)—R₂)—CH₂—O—)_(n)—R′₂;—(CH₂)_(n)—R₂; —CH₂—CH(OR₂)—CH₂—O—(CH₂)_(n)—R′₂;—CH₂—CH(OR₂)—CH₂—O—(CH₂)_(k)—OR′₂; R₂ and R′₂, independently of oneanother are R_(x) if attached to a carbon atom and are R_(y) if attachedto an oxygen atom; k 2 to 20; n 0 to 20; m 0 to 20; R_(x) is hydrogen;hydroxyl; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl; C₁-C₂₀alkoxy;C₄-C₁₂cycloalkoxy; or C₄-C₁₂cycloalkyl or C₄-C₁₂cycloalkoxy each ofwhich is interrupted by oxygen; C₆-C₁₂aryl; pyridyl; pyrimidinyl;triazinyl; pyrrolyl; furyl; thiophenyl; quinolyl; —OR_(z); NHR_(z);R_(z); CONR′R″; C₂-C₂₀alkenyl; C₄-C₁₂cycloalkenyl; C₄-C₁₂cycloalkenylwhich is interrupted by oxygen; or C₃-C₂₀alkynyl; or is any ofC₂-C₂₀alkyl, C₄-C₁₂cycloalkyl, C₂-C₂₀alkoxy, C₄-C₁₂cycloalkoxy,C₄-C₁₂cycloalkyl or C₄-C₁₂cycloalkoxy interrupted by oxygen, C₆-C₁₂aryl,hetero-C₃-C₁₂aryl, C₃-C₂₀alkenyl, cyclohexenyl, which is substituted byhydroxyl, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, cyclohexyl, cyclohexyloxy, phenyl,acetyl, acetyloxy, carboxyl, acryloxy, acrylamino, methacryloxy,methacrylamino; R_(y) is hydrogen; C₁-C₂₀alkyl; C₄-C₁₂cycloalkyl;C₄-C₁₂cycloalkyl which is interrupted by oxygen; C₆-C₁₂aryl; pyridyl;pyrimidinyl; triazinyl; pyrrolyl; furyl; thiophenyl; quinolyl; R_(z);C₂-C₂₀alkenyl; C₄-C₁₂-cycloalkenyl; C₄-C₁₂-cycloalkenyl which isinterrupted by oxygen; or C₃-C₂₀alkynyl; or is any of C₂-C₂₀alkyl,C₄-C₁₂cycloalkyl, C₃-C₁₂alkenyl, C₄-C₁₂-cycloalkenyl, or phenyl, whichis substituted by hydroxyl, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, cyclohexyl,cyclohexyloxy, phenyl, acetyl, acetyloxy, carboxyl, acryloxy,acrylamino, methacryloxy, methacrylamino; R_(z) is —COR′; —COOR′;—CONR′R″; —CO—CH═CH₂; —CO—C(CH₃)═CH₂; R′ and R″ independently of oneanother are hydrogen; C₁-C₂₀alkyl; C₄-C₅₀alkyl which is interrupted byoxygen; C₄-C₁₂cycloalkyl; C₄-C₁₂cycloalkyl which is interrupted byoxygen; C₂-C₂₀alkenyl; C₄-C₂₀alkenyl which is interrupted by oxygen; orC₆-C₁₂aryl; or are any of C₂-C₂₀alkyl, C₄-C₅₀alkyl interrupted byoxygen, C₄-C₁₂cycloalkyl, C₃-C₁₂alkenyl, or phenyl, which is substitutedby hydroxyl, C₁-C₂₀alkyl, C₁-C₂₀alkoxy, cyclohexyl, cyclohexyloxy,phenyl, acetyl, acetyloxy, carboxyl, acryloxy, acrylamino, methacryloxy,methacrylamino.
 3. A compound as claimed in claim 1 of the formula

in which R₁, R₆, R₈, R₁₂ and R₁₄, independently of one another, arehydrogen; C₁-C₂₀alkyl; or halogen; X is hydrogen; C₁-C₂₀alkyl;CHR₂—COOR₂′; or CH₂—CH(OR₂)—CH₂—OR₂′; R₂ and R₂′ independently are H orC₁-C₂₀alkyl; and q is
 0. 4. A compound as claimed in claim 3, wherein informula (4) R₁, R₆, R₈, R₁₂ and R₁₄ are hydrogen; X is C₁-C₂₀alkyl;CHR₂—COOR₂′; or CH₂—CH(OR₂)—CH₂—OR₂′; and q is
 0. 5. A method ofincreasing the sun protection factor of textile fiber materials, whichcomprises applying a compound according to claim 1 in an aqueous oraqueous-organic solution to the fiber materials and then fixing thiscompound.
 6. A method of increasing the sun protection factor of textilefiber materials, which comprises applying a compound according to claim2 in an aqueous or aqueous-organic solution to the fiber materials andthen fixing this compound.
 7. A method of increasing the sun protectionfactor of textile fiber materials, which comprises applying a compoundaccording to claim 3 in an aqueous or aqueous-organic solution to thefiber materials and then fixing this compound.
 8. A method of increasingthe sun protection factor of textile fiber materials, which comprisesapplying a compound according to claim 4 in an aqueous oraqueous-organic solution to the fiber materials and then fixing thiscompound.